CN1348456A - Phthalocyanine compounds, water-base ink compositions and coloured products - Google Patents
Phthalocyanine compounds, water-base ink compositions and coloured products Download PDFInfo
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- CN1348456A CN1348456A CN00806641A CN00806641A CN1348456A CN 1348456 A CN1348456 A CN 1348456A CN 00806641 A CN00806641 A CN 00806641A CN 00806641 A CN00806641 A CN 00806641A CN 1348456 A CN1348456 A CN 1348456A
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- phthalocyanine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/22—Obtaining compounds having nitrogen atoms directly bound to the phthalocyanine skeleton
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
Abstract
Novel phthalocyanine compounds or salts thereof, which have hues suitable for ink-jet recording and are excellent in the light resistance and fastness of records and useful as black colorants or the like; ink compositions containing the same; methods for ink-jet recording by using the compositions; cases in which the compositions are put; ink-jet printers fitted with the cases; and products colored with the colorants. The novel phthalocyanine compounds or salts can be easily prepared by reacting an aminophthalocyanine with (meth)acrylic acid.
Description
Technical field
The present invention relates to a kind of new phthalocyanine compound, contain the water-based ink composition of this compound salt and the colored article that uses said composition.
Background of the present invention
Using the method for ink-jet printer record, is a kind of typical method in the different colour record, comprises generating ink droplet and attached to the different recording material that is used to write down (for example paper, film and cloth).In recent years, because the printhead of this ink-jet printer do not contact with recording materials, thereby there is not noise, and, this ink-jet printer can easily dwindle outside dimension, and high speed operation also carries out colour print like a cork, and makes this method popularize rapidly and can propagate in continuation in the future.The water-based ink that has dissolved a kind of water-soluble dye in a kind of aqueous medium has been used as the ink of fountain pen or felt pen (felt pen) and ink vapo(u)r recorder, wherein can add water miscible organic solvent usually and block at nib or inkjet nozzle place to prevent ink as medium.Water-based ink should be able to provide satisfied density of image, can not block at nib or inkjet nozzle place, and is dry rapidly on recording materials, and good preservation stability does not take place to blur and have.The image that also requires to be provided has satisfied photostabilization and water tolerance.
Because black ink both had been used for monochrome image and also has been used for full-colour image, therefore, in the ink by the prepared different color of different dyestuffs, black is most important.Be disclosed in many application documents (day disclosure special permission communique No.144067/1980 for example as the dyestuff of black ink, day disclosure special permission communique No.207660/1982, day disclosure special permission communique No.147470/1983, day disclosure special permission communique No.93766/1984, day disclosure special permission communique No.190269/1987, day disclosure special permission communique No.246975/1987, day disclosure special permission communique No.22867/1988, day disclosure special permission communique No.33484/1988, day disclosure special permission communique No.93389/1989, day disclosure special permission communique No.140270/1990, day disclosure special permission communique No.167270/1991, day disclosure special permission communique No.200852/1991, day disclosure special permission communique No.359065/1992, day disclosure special permission communique No.172668/1994, day disclosure special permission communique No.248212/1994, day disclosure is speciallyyed permit communique No.26160/1995 and day disclosure special permission communique No.268256/1995).But also can satisfy above-mentioned requirements on the market without any black ink.
Ink-jet printer is widely used as minimized office printer and large scale industry printer.Therefore, what intensive required to be used for this type of ink-jet printer has excellent water tolerance and a sunproof ink, particularly when printed material is common paper.Yet,, still can satisfy above-mentioned requirements without any black ink although there is very big demand.On the other hand, by will such as cellular silica, alumina sol and a kind of from ink the inorganic particulate such as special ceramics of absorbing dye and a kind of cationic polymers or PVA resin together be coated in the water tolerance that significantly improves paper on the paper, this paper through processing can obtain by multiple channel on market as the coated paper of ink-jet printer.
However, the water tolerance of aqueous black ink is still not as paint ink.Therefore, need that invention is a kind of to have the water-proof black dyes and the ink of peer-level with paint ink.Improve its sunproof technology and also do not develop, remain the problem that needs solve.
The chemical structure of black colorant of water-based ink that is used for ink-vapor recording is by a kind of azo product, for example a kind of diazonium product, nitrine product or tetrazo product representative.Though the azo product has water tolerance relatively preferably, photostabilization is not as the cyano group dyestuff by the copper phthalocyanine representative.Therefore, the aqueous black ink obtains by several colorant combination that will have advantageous property respectively usually.
Even an object of the present invention is to provide black colorant and aqueous black ink that a kind of use separately also has the black colourity of suitable ink-vapor recording; On the water tolerance of recording picture and photostabilization, be equal to paint ink; And the barcode that can use near infrared ray identification to print.
Of the present invention open
The present inventor addresses the above problem to have carried out hard research, found that a kind of phthalocyanine compound that contains carbonyl, finished the present invention, this compound is the amino phthalocyanine and (methyl) vinylformic acid (vinylformic acid and/or methacrylic acid of general formula (1) representative shown in hereinafter, hereinafter use with the same meaning) reaction product or its salt, and have the character that satisfies above-mentioned purpose.
That is of the present invention theing contents are as follows:
1. a phthalocyanine compound or its salt are obtained by the amino phthalocyanine and the reaction of (methyl) vinylformic acid of general formula as follows (1) representative.
(in general formula (1), M represents two hydrogen atoms or an atoms metal, and m is the integer smaller or equal to 4).
2. a kind of alkali-soluble phthalocyanine compound or its salt of general formula as follows (3) representative,
(in general formula (3), R
1, R
2, R
3And R
4Represent following arbitrary group: NHC independently of each other
2H
4COOH, N (C
2H
4COOH)
2, NHCH
2CH (CH
3) COOH, N (CH
2CH (CH
3) COOH)
2And NH
2M represents two hydrogen atoms or an atoms metal; N, p, q and r represent 0 or 1, and condition is that n+p+q+r is 1 to 4), this compound is obtained with the reaction of (methyl) vinylformic acid by the amino phthalocyanine of general formula as follows (2) representative.
(in general formula (2), M, n, p, q represents respectively and the identical implication of general formula (3) with r).
3. the phthalocyanine compound in above-mentioned the 1st or 2 or its salt, wherein said atoms metal are nickel, copper, zinc, aluminium, iron or cobalt.
4. phthalocyanine compound or its salt in above-mentioned the 3rd, wherein said atoms metal is a copper.
5. the salt of the phthalocyanine compound in above-mentioned the 2nd, wherein said salt is an alkali metal salt that the solubleness in water is equal to or higher than 2 weight %.
6. the water-based ink composition that contains the phthalocyanine compound salt in above-mentioned the 2nd.
7. the water-based ink composition in above-mentioned the 6th, wherein said salt is alkanol amine salt, lithium salts, sodium salt, sylvite or ammonium salt.
8. the water-based ink composition in above-mentioned the 6th, wherein said salt is ammonium salt.
9. the water-based ink composition in above-mentioned the 6th wherein also comprises water and water miscible organic solvent.
10. the water-based ink composition in above-mentioned the 6th, wherein said water-based ink composition contains the inorganic salt that are equal to or less than 1 weight %.
11. the water-based ink composition in above-mentioned the 6th, wherein said water-based ink composition is used to ink-vapor recording.
12. the method for an ink-vapor recording is characterized in that using water-based ink composition in above-mentioned the 6th as the ink in this ink jet recording method, according to the response to recording signal ink droplet is sprayed on the recording materials.
13. the ink jet recording method in above-mentioned the 12nd, wherein said recording materials are that a kind of information is transcribed sheet.
14. contain the container of the water-based ink composition in above-mentioned the 6th.
15. have the spray ink Printing machine equipment of above-mentioned the 14th container.
16. contain the phthalocyanine compound in above-mentioned the 2nd or the colored article of its salt.
Simple description to accompanying drawing
Fig. 1 represents the embodiment of the invention 1 absorption spectrum to 4 compounds that obtained that gone out by spectrophotometer measurement.
Fig. 2 is illustrated in the embodiments of the invention 2, the visible light of initial compounds in same solvent (before the reaction) and product compound (reaction back).
Fig. 3 represents the infrared spectra of employed amino phthalocyanine compound in the embodiments of the invention 2.
Fig. 4 represents the infrared spectra of the phthalocyanine compound that obtained in the embodiments of the invention 2.
Implement best mode of the present invention
Phthalocyanine compound of the present invention (if no special instructions, hereinafter comprising its salt) can obtain by amino phthalocyanine and the reaction of (methyl) acrylic acid. This compound is regarded as the amino and the compound that the reaction of (methyl) acrylic acid produces by amino phthalocyanine compound, is actually all or part of carboxylic ethamine group (or carboxymethyl ethylamino-) that changes into of the amino group that is combined on the phthalocyanine structure. Because new phthalocyanine compound of the present invention has dissolubility good in alkaline aqueous solution and good fastness under given conditions, therefore be used as novel colouring agent, particularly black colorant or black dyes.
Phthalocyanine compound of the present invention is considered to contain the compound of general formula (3) representative as main component, because known carboxylic group and vinyl reaction, therefore also contain accessory substance, this accessory substance is formed by the continuation reaction after amino phthalocyanine and the reaction of (methyl) acrylic acid are finished of the carboxylic group of the phthalocyanine that has formed and (methyl) acrylic acid vinyl. Even contain this type of accessory substance, phthalocyanine compound of the present invention still can be used as composition for ink.
Phthalocyanine compound of the present invention for example can react amino phthalocyanine in a kind of solvent and acrylic or methacrylic acid by heating and produce in a kind of solvent. The initiation material acrylic or methacrylic acid of reaction also can be used as solvent. (methyl) acrylic acid consumption as solvent can be the requirement of mixing with amino phthalocyanine under stirring condition. This consumption includes but not limited to 3 times of amino phthalocyanine quality or higher, from considering that economically preferred 3-10 doubly.
Employed other solvents must be inertia on substantially to acrylic acid and methacrylic acid, include but not limited to acetic acid, DMF, methyl-sulfoxide and 1-METHYLPYRROLIDONE. The consumption of other solvents can be the requirement of mixing with amino phthalocyanine, acrylic acid and/or methacrylic acid under stirring condition, if mix with a large amount of acrylic acid and/or methacrylic acid, also can reduce the consumption of solvent. This consumption includes but not limited to identical in quality or more with amino phthalocyanine, and preferred 1-8 doubly. The molal quantity of employed acrylic acid and/or methacrylic acid can be equal to or higher than the molal quantity of existing whole amino groups in the amino phthalocyanine in this case. Consider that from control reaction speed and the angle that reduces unreacted initiation material this consumption includes but not limited to 2 times of preferred amino phthalocyanine quality or higher, more preferably 2-10 doubly.
Preferred reaction is carried out under the temperature of avoiding acrylic or methacrylic acid generation thermal polymerization, and for example 30 ℃-140 ℃, more preferably 60 ℃-120 ℃. If but allowed to exist acrylic or methacrylic acid polymerizate impurity, then temperature would be not limited to above-mentioned scope. Can use a kind of known polymerization inhibitor such as first quinone and quinhydrones to avoid occuring polymerization. Oxygen equally also can be used as effective polymerization inhibitor, therefore can be blown into air in reaction system.
The normally a kind of free acid of compound or its salt that so synthesize. For example can obtain free acid by acid the separation. Can by common salt switching method, for example by in the free acid of this compound, adding corresponding organic or inorganic alkali salt be converted to other desired salt. Organic or inorganic alkali includes but not limited to a kind of alkanolamine (preferred C1-C
6Single, two or three lower alkanes hydramine, more preferably C2-C
3Two alkanolamines), for example diethanol amine and triethanolamine; A kind of alkali metal hydroxide is such as lithium hydroxide, NaOH and potassium hydroxide; Ammonium hydroxide and a kind of water soluble salt comprise alkali carbonate, for example lithium carbonate, sodium carbonate and potash. Add also insoluble product of organic or inorganic alkali even can filter. The solubility of alkali metal salt in water of preferred phthalocyanine compound of the present invention is 2 % by weight or higher, more preferably 3 % by weight or higher.
Obtain to be insoluble to the phthalocyanine compound of the present invention of acrylic or methacrylic acid by reaction. Therefore, the solvent that can be used as next time reaction of the filtrate behind the separated product is reused.
Because the amino phthalocyanine as raw material does not contain at 1700cm-1Near the carbonyl of very strong absworption peak is arranged, therefore, can detect the phthalocyanine compound of the present invention that produces by infrared absorption spectroscopy.
Different from the amino phthalocyanine as raw material, the phthalocyanine compound that so obtains is alkali-soluble, black and has the character of black dyes. Comprehensive consideration to the physics and chemistry character of the reactivity that comprises initiation material shows, although only by its physics and chemistry character this point can not be described clearly, but, from comprehensive consideration of the physics and chemistry character of the reactivity that comprises initiation material, main at least product is estimated to be the phthalocyanine compound of general formula (3) representative.
Even contain above-mentioned accessory substance or with the phthalocyanine compound that does not reduce nitro described below, as long as it has the character of dyestuff of the present invention, the phthalocyanine compound that so obtains still comprises within the scope of the invention.
The amino phthalocyanine that is used as general formula (1) representative of raw material can be improved one's methods synthetic by known method or its. For example, method according to known synthetic phthalocyanine, use in accordance with the appropriate ratio phthalic anhydride and 4-nitrophthalic acid and heating, until in the presence of urea and catalyst (for example copper powder), react, by the synthetic phthalocyanine with nitro of known method, then its reduction is generated amino phthalocyanine. If under the condition that does not have metal or slaine, react, phthalic anhydride and 4-nitrophthalic acid generate the compound of general formula (1) representative, wherein M represents two hydrogen atoms, if react under the condition that metal or slaine are arranged, the M in the compound of the general formula that then generates (1) representative represents corresponding metal. M mean value in the general formula (1) is 4 or less, can change according to the ratio of phthalic anhydride and 4-nitrophthalic acid. If amino phthalocyanine can in the center with a coordination metal and with the coordination metal, can have better heat-resisting and light resistance on the whole. Metal M includes but not limited to iron, cobalt, nickel, copper, zinc, aluminium and lead. The raw material that is used as C.I.Sulphur Green 14 with copper as the amino phthalocyanine of metal M.
The amino phthalocyanine that uses as phthalocyanine compounds raw material of the present invention can obtain by reducing the nitro of corresponding nitro compound. In addition, even amino phthalocyanine contains the nitro that part is not reduced, the raw material that still can be used as phthalocyanine compound of the present invention uses, as long as it does not consist of substantial obstacle to the present invention. Can be by the ESI Mass Spectrometer Method nitro of the compound that obtains.
Water-based ink composition of the present invention is a kind of aqueous solution that has dissolved the water soluble salt of phthalocyanine of the present invention in water or water-soluble solvent (a kind of organic solvent of moisture water-soluble or water-miscible). Be suitable for water-based ink composition phthalocyanine of the present invention water soluble salt usually the solubility in water be 2 quality % or higher, preferred 3 quality % or higher, more preferably 5 quality % or higher. Preferred salt comprises alkanol amine salt, alkali metal salt and ammonium salt. The pH value of preferred ink is 6-11. If as the ink of ink-jet printer, then water-based ink composition contains a kind of inorganic material, such as chloride or the sulfate of metal sun example, preferably its content is as far as possible little, for example, accounts for 1% or lower ratio in composition. Can wash product with water, obtain to contain the phthalocyanine compound as water-based ink composition of the present invention of being suitable for of a small amount of inorganic matter. The colouring agent of the present invention that contains the inorganic matter of less amount for preparation, product is desalted for example by conventional inverse osmosis, or the mixed solvent of the dry products of colouring agent of the present invention or wet cake and water and alcohol as methyl alcohol stirred, then filter and drying.
Water-based ink composition of the present invention is by making water prepare as medium. The amount that contains phthalocyanine of the present invention or its salt in the water-based ink composition is preferably the 0.1-20 % by weight, more preferably 1-10 % by weight, more preferably 2-8 % by weight. Water-based ink composition of the present invention can further contain the water-miscible organic solvent of 0-30 % by weight, the ink modulator of 0-5 % by weight, and all the other components are water.
Composition for ink of the present invention is by with compound or its salt of the present invention, if necessary, with described water-miscible organic solvent hereinafter and for the preparation of the additive of ink at pure water, prepare as mixing in the distilled water. Compound or its salt of the present invention can be water-soluble, hereinafter in described water-miscible organic solvent and the mixture for the preparation of the additive of ink. If necessary, composition for ink of the present invention can be filtered and remove impurity.
Described water-miscible organic solvent comprises C1-C
4Alkanol, for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol (IPA), butanols, isobutanol, sec-butyl alcohol and the tert-butyl alcohol; Acid amides (preferred C1-C
3Low carbon chain acyl group N-list or N, N-two-C1-C
3Alkylamine), such as DMF and DMA; Lactams (preferred 4-7 membered lactams) is such as epsilon-caprolactams and NMP (1-METHYLPYRROLIDONE); The ring-type urea (preferably is with selectively C1-C
35-6 person's ring-type urea of alkyl substituent) such as 1,3-methylimidazole quinoline-2-ketone and 1,3-dimethyl hexahydro-pyrimidine-2-ketone; Ketone or keto-alcohol (preferred C3-C
6Ketone or keto-alcohol), such as acetone, methyl ethyl ketone and 2-methyl-2 hydroxyl penta-4-ketone; Cyclic ether (preferred 5-6 person's cyclic ether) is such as oxolane and dioxane; Such as ethylene glycol, second sulfo-glycol, 1,2-or 1,3-PD, 1,2 or BDO, 1,6-hexylene glycol, diethylene glycol (DEG), triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol and polypropylene glycol etc. are with C2-C
6The monomer of the aklylene glycol of alkylidene unit or alkylidene thioglycol, oligomer or polymer (PAG or polyalkylene mercaptoacetate); Polyalcohol (preferred C1-C
6Trihydroxylic alcohol), such as glycerine and 1,2,6-hexanetriol; (the C of polyalcohol1-C
4) alkyl ether is (preferably with the (C of 1-3 hydroxyl2-C
3) (the C of polyalcohol1-C
4) alkyl ether), such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether (BC), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether and triethylene glycol list ether; Gamma-butyrolacton; And methyl-sulfoxide.
Additive comprises anticorrisive agent, pH adjusting agent, chelating agent, antirust agent, Water-soluble UV-absorbents, water-soluble polymeric compound, dyestuff lytic agent, surfactant and other additives for the preparation of ink.
Anticorrisive agent comprises dehydro sodium acetate, sodium sorbate, 2-pyridine mercaptan-1-sodium oxide molybdena, Sodium Benzoate and penta sodium pentachlorophenate.
The pH regulator agent comprises any material that the pH value of ink can be controlled in 6 to 11 scopes, as long as it does not have a negative impact to the preparation of ink.The example is an alkanolamine, as diethanolamine and trolamine; Alkali metal hydroxide, as lithium hydroxide, sodium hydroxide and potassium hydroxide; Ammonium hydroxide or alkaline carbonate, as Quilonum Retard, yellow soda ash and salt of wormwood.Especially, if regulate the pH of water-based ink composition of the present invention with ammonium hydroxide, then this composition for ink can provide a kind of and has good water-proof printed matter, because ammonium ion enters in the printed material as ammonia when printing.
Sequestrant comprises sodium ethylene diamine tetracetate, B,EDTA, hydroxyethylethylene diamine tri-acetic acid sodium, diethylene triaminepentaacetic acid(DTPA) sodium and uridylic (uracyl) sodium diacelate.
Rust-preventive agent comprises acid sulfoxylate, Sulfothiorine, ammonium mercaptoacetate, nitrous acid di-isopropyl ammonium, trinitrol and nitrous acid dicyclohexyl ammonium.
The water-soluble polymeric compound comprises polyvinyl alcohol, derivatived cellulose, polyamine and poly-imines.
Water-soluble UV light absorber comprises sulfonation benzophenone and sulfonated benzimidazole triazole.
The dyestuff solvating agent comprises ε-Ji Neixianan, ethylene carbonate and urea.
Tensio-active agent comprises the known negatively charged ion of the public, positive example or nonionogenic tenside.
The recording materials (body material) that are used for ink jet recording method of the present invention comprise that information transcribes sheet, as paper and film, and Mierocrystalline cellulose and leather.Preference information is transcribed sheet to be surface treated and in fact to contain ink receiving layer on body material.Ink receiving layer can be provided, for example by on above-mentioned body material, soak into or apply a kind of positive example polymkeric substance or with a kind of can be from ink inorganic fine powder such as cellular silica, alumina sol and special pottery and a kind of hydrophilic polymer of absorbing dye, be coated in together on the surface of above-mentioned body material as polyvinyl alcohol and polyvinylpyrrolidone.The sheet that has an ink receiving layer is commonly called ink-jet speciality paper (film) or satin paper (film) and can buys on market, Pictorico (byAsahi Glass KK) for example, Color BJ Paper, colored BJ photographic film (by Canon KK), coloured image ink-jet speciality paper (by Sharp KK), super special big smooth print film (by SeikoEpson KK) and Pictafine (by Hitachi Maxell KK).Ink jet recording method certainly is used for common paper.
Water-based ink composition of the present invention removes and to contain phthalocyanine compounds beyond the region of objective existence of the present invention, can also contain one or more other compounds be suitable for printing, duplicating, mark, write, draw, impression and record, particularly ink-vapor recording.This kind composition can provide a kind of and have high-density and high-quality black printing product aspect water tolerance, photostabilization and resistance to abrasion.Phthalocyanine compound of the present invention particularly has better water tolerance and photostabilization on the speciality paper of ink-vapor recording in common paper.
Because its highly water-soluble, water-based ink composition of the present invention can be owing to sedimentation is separated in storage process.Even (recycling for a long time or the intermittent type use) also can not form the change of blocking and can not show physical properties at nozzle if water-based ink composition of the present invention is used for ink-jet printer use in the long relatively time, as decomposing or the reduction colo(u)r pick-up.
Container of the present invention contains above-mentioned water-based ink composition.The container of the present invention that contains water-based ink composition has been installed in the ink cartridge parts in the ink-jet printer of the present invention.Articles colored phthalocyanine compound or its salt that has used the invention described above of the present invention preferably uses above-mentioned water-based ink composition painted.
Water-based ink composition of the present invention has the approaching desirable black of standard with JAPAN COLOR of JNC (Japanese printing machinery make association), shows stable black and its tinctorial property is good under different light sources.And, if water-based ink composition of the present invention has good photostabilization and water-proof magenta, cyan or yellow common use a kind of have good photostabilization and water-proof chromatograp can be provided with known.
Phthalocyanine compound of the present invention has high absorbance in the near-infrared region, therefore is suitable for printing the barcode of being read by near infrared light, makes water-based ink composition of the present invention very useful.
Embodiment
Hereinafter the present invention will be described in further detail in conjunction with the embodiments.If no special instructions, " part " hereinafter and " % " all represent weight.
Copper phthalocyanine and 100 parts of vinylformic acid addings of 20 parts of per molecules on average being had 3.2 amino groups have in the four neck flasks of condenser, in oil bath temperature are increased to 75 ℃ and lasting 1 hour then, stir 12 hours under same temperature.Reaction soln is cooled to 40 ℃ and use Nutsche funnel filtering separation product,, obtains 26.2 parts of black phthalocyanine compounds with 1000 parts 60 ℃ water cleaning down product, drying.So the total amount of the inorganic salt that compound contained that obtain is 0.4501% (NaCl 0.0391% and Na
2SO
40.4110%).The solubleness of the ammonium salt of compound in water is 8%, and maximum absorption band under the concentration of 0.05g/1000ml (in the ion exchanged water) (λ max) is 687.2nm.
Embodiment 2
20 parts of per molecules are on average had the copper phthalocyanine of 3.2 amino groups and 100 parts of vinylformic acid and 0.5 part of quinhydrones add and have in the four neck flasks of condenser, in oil bath, temperature is increased to 90 ℃ and continue 1 hour then, under same temperature, stirred 6 hours.Reaction soln is cooled to 40 ℃ and use Nutsche funnel filtering separation product,, obtains 27.9 parts of black phthalocyanine compounds with 1000 parts 60 ℃ water cleaning down product, drying.So the total amount of the inorganic salt that compound contained that obtain is 0.0984% (NaCl 0.0320% and Na
2SO
40.0664%).The solubleness of the ammonium salt of this compound in water is 10%, and maximum absorption band under the concentration of 0.05g/1000ml (in the ion exchanged water) (λ max) is 732.8nm.
Embodiment 3
The copper phthalocyanine that 20 parts of per molecules is on average had 3.2 amino groups, 85 parts of acetate, 25 parts of vinylformic acid and 0.5 part of quinhydrones add and have in the four neck flasks of condenser, in oil bath temperature are increased to 115 ℃ and lasting 1 hour then, stir 2 hours under same temperature.Reaction soln is cooled to 40 ℃ and use Nutsche funnel filtering separation product,, obtains 25.9 parts of black phthalocyanine compounds with 1000 parts 60 ℃ water cleaning down product, drying.So the total amount of the inorganic salt that compound contained that obtain is 0.8573% (NaCl 0.0333% and Na
2SO
40.8240%).The solubleness of the ammonium salt of this compound in water is 7%, and maximum absorption band under the concentration of 0.05g/1000ml (in the ion exchanged water) (λ max) is 682.8nm.
Embodiment 4
Do not reduce the amino phthalocyanine of cupric coordination of nitro with 20 parts by reduction per molecule containing of having on average that the copper phthalocyanine of 4.0 nitryl groups obtains, 100 parts of vinylformic acid and 0.5 part of quinhydrones add and have in the four neck flasks of condenser, in oil bath, temperature is increased to 90 ℃ and lasting 1 hour then, under same temperature, stirred 6 hours.Reaction soln is cooled to 40 ℃ and use Nutsche funnel filtering separation product,, obtains 32.1 parts of black phthalocyanine compounds with 1000 parts 60 ℃ water cleaning down product, drying.So the total amount of the inorganic salt that compound contained that obtain is 0.9120% (NaCl 0.4030% and Na
2SO
40.5090%).The solubleness of the ammonium salt of this compound in water is 10%, and maximum absorption band under the concentration of 0.05g/1000ml (in the ion exchanged water) (λ max) is 750.0nm.
The ESI mass spectrum of the compound that embodiment 4 is obtained shows that it contains vinylformic acid and the adduction product that has the amino phthalocyanine of remaining nitro.The measurement of absorption spectrum
The ammonium salt of the compound that obtained in the foregoing description is dissolved in the solution of its 0.05g/1000ml of preparation in the ion exchanged water respectively, uses UV-2200 spectrophotometer (ShimazuSeisakusyo KK manufacturing) to measure its absorption spectrum.Its absorption spectrum is shown among Fig. 1.
The ammonium salt of the amino phthalocyanine compound of the present invention that embodiment 2 employed raw material phthalocyanine compounds and embodiment 2 are obtained is dissolved in mixed solvent (DMF: 2.8% ammoniacal liquor=1: 1) prepare its 0.05g/1000ml solution, measure its absorption spectrum according to the mode identical with Fig. 1 respectively.Its absorption spectrum is shown among Fig. 2.
The infrared absorption spectrum of the phthalocyanine compound of the present invention that amino phthalocyanine compound of embodiment 2 employed raw materials and embodiment 2 are obtained is shown among Fig. 3 and Fig. 4.
The absorption spectrum of Fig. 2 shows amino phthalocyanine compound of raw material and vinylformic acid reaction.The infrared absorption spectrum of Fig. 3 and Fig. 4 shows and exists alkyl to absorb (3000cm in the compound that embodiment 2 obtained
-1) and carbonyl absorption (1700cm
-1) and confirm that vinylformic acid is introduced in the molecule.
Embodiment 5
(A) preparation of ink
Prepare composition solution according to following description and also filter with the filtering membrane of 0.45 μ m, preparation is used for the water-based ink composition of ink-jet.Use ion exchanged water.Making water and ammonium hydroxide prepare water-based ink composition, to make its pH be 8-10, and total amount is 100 parts.
Table 1
The tinting material that is obtained (desalination product) is 5.0 parts in the above-described embodiments
5.0 parts of glycerine
5.0 parts in urea
4.0 parts of N-N-methyl-2-2-pyrrolidone N-s
3.0 parts of IPA (Virahol)
2.0 parts of diethylene glycol monobutyl ethers
76.0 parts in water and ammonium hydroxide
100.0 parts of total amounts
So the inorganic salt content in the water-based ink composition that obtains is as follows:
Composition for ink contains the compound of embodiment 1: 0.02251%
Composition for ink contains the compound of embodiment 2: 0.00492%
Composition for ink contains the compound of embodiment 3: 0.04289%
Composition for ink contains the compound of embodiment 1: 0.04560%
(B) spray ink Printing
By using ink-jet printer (trade(brand)name: PICTY80L, NEC KK makes) on three kinds of recording papers, carry out ink-vapor recording, three kinds of recording papers are respectively: common paper (A4 printer paper, TLB5A4S, Canon KK makes), speciality paper A (Color BJ Paper LC101, Canon KK makes), speciality paper B (Color Image Jet Coat Paper STX73A4, Sharp KK makes).The test result of colourity, photostabilization, water tolerance and the tinctorial property of the recording picture of water-based ink composition of the present invention (compound that contains embodiment 1 and 2) is shown in Table 2.
The composition for ink of two kinds of Comparative Examples of preparation makes optical density(OD) consistent with the black ink of the present invention in above-mentioned (A) item, but each composition for ink contains C.I.Direct black 19 (being represented by following general formula) respectively, and a kind of compound (being represented by following general formula) (Comparative Examples 2) that is generally used for the nitrogenous tinting material (Comparative Examples 1) of black ink-jet tinting material and describes in day disclosure special permission communique No.140270/1990 replaces tinting material.The test result of colourity, photostabilization, water tolerance and the tinctorial property of the image that composition for ink write down of Comparative Examples also is shown in Table 2.
Comparative Examples 1
Comparative Examples 2
(C) to the evaluation of document image
(1) colourity is judged
The colourity of recording picture and sharpness:
Use GRETAG SPM50 (GRETAG KK manufacturing) that the recording picture that is depicted on the recording materials is carried out colorimetric measurement, calculate L
*, a
*And b
*Value.
(2) photostabilization
Use carbon arc fugitometer (Suga Testing Machine KK manufacturing) on recording picture, to shine carbon arc 20 hours.With the described blue colour gradation of JIS L-0814 serves as that grade is determined on the basis.Pre-irradiation and postradiation aberration (△ E) are also determined by above-mentioned colorimetric system.
(3) water tolerance
Recording materials are placed the beaker of filling water, stirred 2 minutes and dry.With the JIS gray scale of fading is the variation that document image is determined on the basis.Before handling with handle after aberration (△ E) also determine by above-mentioned colorimetric system.
(4) tinctorial property
Determine that by vision recording picture is from the chromaticity distortion under the tungsten lamp of standard light source.
Zero: the slight deviation of colourity
△: the moderate deviation of colourity
*: the height tolerance of colourity
The results are shown in the table 2 of above-mentioned (1)-(4).
(5) reflectivity curve
Use COMSEK-V colorimetric system (Nippon Kayaku KK manufacturing) to estimate document image and draw reflectivity curve with colorimetry.The results are shown in the table 3 of reflectivity.
Table 2
| Recording materials | Colourity | Photostabilization | Water tolerance | Tinctorial property | ||
| ??L * | ??a * | ??b * | Estimate (△ E) | Estimate (△ E) | ||
| Common paper | ??37.9 | ??-0.8 | ??-2.9 | Class 4 (2.6) | Class 5 (1.0) | ???○ |
| Speciality paper A | ??28.7 | ??0.1 | ??-5.1 | Grade 3-4 (4.5) | Class 5 (1.9) | ???○ |
| Speciality paper B | ??20.3 | ??-0.5 | ??-4.5 | Grade 3-4 (4.5) | Class 5 (0.7) | ???○ |
Embodiment 2
| Recording materials | Colourity | Photostabilization | Water tolerance | Tinctorial property | ||
| ??L * | ????a * | ????b * | Estimate (△ E) | Estimate (△ E) | ||
| Common paper | ??34.5 | ????0.2 | ????-1.2 | Class 4 (2.0) | Class 5 (1.1) | ???○ |
| Speciality paper A | ??24.6 | ????1.1 | ????-4.5 | Class 4 (4.5) | Class 5 (0.9) | ???○ |
| Speciality paper B | ??16.9 | ????-0.3 | ????-2.1 | Class 4 (2.7) | Class 5 (0.9) | ???○ |
Embodiment 3
| Recording materials | Colourity | Photostabilization | Water tolerance | Tinctorial property | ||
| ??L * | ???a * | ???b * | Estimate (△ E) | Estimate (△ E) | ||
| Common paper | ??45.2 | ???-3.8 | ???-2.3 | Class 4 (2.3) | Class 5 (0.9) | ??○ |
| Speciality paper A | ??34.4 | ???-3.3 | ???-5.3 | Grade 3-4 (3.9) | Class 5 (2.0) | ??○ |
| Speciality paper B | ??28.0 | ???-4.3 | ???-5.8 | Grade 3 (6.8) | Class 5 (1.2) | ??○ |
Embodiment 4
| Recording materials | Colourity | Photostabilization | Water tolerance | Tinctorial property | ||
| ??L * | ???a * | ????b * | Estimate (△ E) | Estimate (△ E) | ||
| Common paper | ??37.2 | ???1.3 | ????0.6 | Class 4 (2.8) | Class 5 (0.9) | ???○ |
| Speciality paper A | ??28.3 | ???2.5 | ????-3.2 | Grade 3 (7.4) | Class 5 (1.2) | ???○ |
| Speciality paper B | ??20.2 | ???1.2 | ????-1.2 | Grade 3-4 (5.7) | Class 5 (1.5) | ???○ |
Comparative Examples 1
| Recording materials | Colourity | Photostabilization | Water tolerance | Tinctorial property | ||
| ??L * | ???a * | ??b * | Estimate (△ E) | Estimate (△ E) | ||
| Common paper | ??35.6 | ???-0.1 | ??-2.3 | Class 4 (2.0) | Grade 2 (11.5) | ??○ |
| Speciality paper A | ??23.0 | ???-2.4 | ??-4.7 | Grade 3-4 (4.1) | Class 4 (2.9) | ??○ |
| Speciality paper B | ??16.4 | ???-0.5 | ??-2.3 | Class 4 (1.5) | Class 4 (2.8) | ??○ |
Comparative Examples 2
| Recording materials | Colourity | Photostabilization | Water tolerance | Tinctorial property | ||
| ?L * | ???a * | ??b * | Estimate (△ E) | Estimate (△ E) | ||
| Common paper | ?29.2 | ???2.9 | ??-6.9 | Class 4 (1.3) | Grade 3 (6.2) | ???△ |
| Speciality paper A | ?21.9 | ???5.4 | ??-5.6 | Grade 3 (8.0) | Class 5 (1.0) | ???△ |
| Speciality paper B | ?15.6 | ???5.1 | ??-3.3 | Class 4 (2.8) | Grade 2 (10.3) | ???△ |
Table 2 shows that the ink itself that contains tinting material of the present invention has black colourity and a kind of document image with good tinctorial property can be provided, no matter all have good water tolerance and photostabilization on common paper and speciality paper.That is to say that this ink can provide stay-in-grade record comprising on any recording materials of common paper.On the other hand, the ink that contains the nitrogenous tinting material of Comparative Examples 1 and 2 has relatively poor water tolerance and shows the unsettled photostabilization of the quality that depends on recording materials on common paper and speciality paper.
Contain the recording picture that the ink of the foregoing description 1-4 compound is provided with the colorimetry evaluation on speciality paper B.Reflectivity to every kind of wavelength (400-700nm) the results are shown in the table 3.Table 3 shows that phthalocyanine tinting material of the present invention itself shows as black.
Table 3
| Wavelength (nm) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Reflectivity (%) | Reflectivity (%) | Reflectivity (%) | Reflectivity (%) | |
| ??400 | ????4.77 | ????4.06 | ????6.09 | ????4.16 |
| ??420 | ????5.37 | ????4.42 | ????7.40 | ????4.35 |
| ??440 | ????5.12 | ????4.05 | ????7.29 | ????3.68 |
| ??460 | ????4.74 | ????3.71 | ????6.93 | ????3.28 |
| ??480 | ????4.50 | ????3.47 | ????6.56 | ????3.09 |
| ??500 | ????4.31 | ????3.31 | ????6.25 | ????3.01 |
| ??520 | ????4.18 | ????3.22 | ????6.05 | ????3.01 |
| ??540 | ????4.12 | ????3.18 | ????5.91 | ????3.10 |
| ??560 | ????4.08 | ????3.17 | ????5.77 | ????3.27 |
| ??580 | ????3.97 | ????3.12 | ????5.46 | ????3.38 |
| ??600 | ????3.67 | ????2.98 | ????4.84 | ????3.33 |
| ??620 | ????3.29 | ????2.74 | ????4.15 | ????3.10 |
| ??640 | ????2.98 | ????2.50 | ????3.64 | ????2.73 |
| ??660 | ????2.89 | ????2.41 | ????3.43 | ????2.47 |
| ??680 | ????2.95 | ????2.45 | ????3.45 | ????2.37 |
| ??700 | ????3.04 | ????2.52 | ????3.56 | ????2.33 |
All The above results show that the black ink that contains phthalocyanine tinting material of the present invention is a kind of good black ink of use range widely that has.
Commercial Application
Phthalocyanine compound of the present invention as having good water miscible novel colouring agent and using is usually expressed as black, can be used as black colorant and it has the permeability good to filter membrane in the production process of composition for ink. In addition, use the composition for ink of the present invention of phthalocyanine compound crystal settling not occurring through after the long term storage, also can not change physical property and color, therefore have good storage stability. When using as the black ink of ink mist recording, composition for ink of the present invention can provide a kind of printed matter with good light resistance and resistance to water. And when using with magenta, cyan and yellow uitramarine, this composition for ink also can provide the ink mist recording product with good light resistance and resistance to water, because said composition is approaching with pigment qualitatively. The surface of printed matter is close to desirable black and have good coloring.
Therefore, ink of the present invention is very useful as a kind of black ink composition for ink mist recording. Water-based ink composition of the present invention can be used for the bar code that printing is read by near infrared ray effectively, because phthalocyanine compound of the present invention has the high absorbance in the near infrared region.
Claims (16)
1. a phthalocyanine compound or its salt are obtained by the amino phthalocyanine and the reaction of (methyl) vinylformic acid of general formula 1 representative as follows,
In general formula 1, M represents two hydrogen atoms or an atoms metal, and m is the integer smaller or equal to 4.
2. a kind of alkali-soluble phthalocyanine compound of general formula 3 representatives as follows or its salt,
In general formula 3, R
1, R
2, R
3And R
4Represent following any group: NHC independently of each other
2H
4COOH, N (C
2H
4COOH)
2, NHCH
2CH (CH
3) COOH, N (CH
2CH (CH
3) COOH)
2And NH
2M represents two hydrogen atoms or an atoms metal; N, p, q and r represent 0 or 1, and condition is that n+p+q+r is any integer of 1 to 4; This compound is obtained with the reaction of (methyl) vinylformic acid by the amino phthalocyanine of following general formula 2 representatives,
In general formula 2, M, n, p, q and r represent the implication identical with general formula 3 respectively.
3. the phthalocyanine compound in the claim 1 or 2 or its salt, wherein said atoms metal is nickel, copper, zinc, aluminium, iron or cobalt.
4. the phthalocyanine compound in the claim 3 or its salt, wherein said atoms metal is a copper.
5. the salt of phthalocyanine compound in the claim 2, wherein said salt is an alkali metal salt that the solubleness in water is equal to or higher than 2 weight %.
6. the water-based ink composition that contains the phthalocyanine compound salt of claim 2.
7. the water-based ink composition in the claim 6, wherein said salt is alkanol amine salt, lithium salts, sodium salt, sylvite or ammonium salt.
8. the water-based ink composition in the claim 6, wherein said salt is ammonium salt.
9. the water-based ink composition in the claim 6 wherein also comprises water and water-miscible organic solvent.
10. the water-based ink composition in the claim 6, wherein said water-based ink composition contains the inorganic salt that are equal to or less than 1 weight %.
11. the water-based ink composition in the claim 6, wherein said water-based ink composition is used to ink-vapor recording.
12. the method for an ink-vapor recording is characterized in that using water-based ink composition in the claim 6 as the ink in this ink jet recording method, according to the response to recording signal ink droplet is sprayed on the recording materials.
13. being a kind of information, the ink jet recording method in the claim 12, wherein said recording materials transcribe sheet.
14. contain the container of the water-based ink composition in the claim 6.
15. have the spray ink Printing machine equipment of the container of claim 14.
16. contain the phthalocyanine compound in the claim 2 or the coloured prod of its salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP119248/99 | 1999-04-27 | ||
| JP11924899 | 1999-04-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1348456A true CN1348456A (en) | 2002-05-08 |
Family
ID=14756637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00806641A Pending CN1348456A (en) | 1999-04-27 | 2000-04-25 | Phthalocyanine compounds, water-base ink compositions and coloured products |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6589325B1 (en) |
| EP (1) | EP1174432A1 (en) |
| KR (1) | KR20020002423A (en) |
| CN (1) | CN1348456A (en) |
| CA (1) | CA2367738A1 (en) |
| WO (1) | WO2000064901A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107835843A (en) * | 2015-07-01 | 2018-03-23 | 日本化药株式会社 | Dispersible pigment dispersion, colored resin composition and optical filter containing organic coloring pigments and infrared absorbing dye |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4190187B2 (en) * | 2002-01-22 | 2008-12-03 | 富士フイルム株式会社 | Ink containing water-soluble phthalocyanine compound, ink-jet ink, ink-jet recording method, and method for improving ozone gas fading of colored image material |
| WO2003074613A1 (en) * | 2002-03-07 | 2003-09-12 | Nippon Kayaku Kabushiki Kaisha | Phthalocyanine compound, water-base ink composition and colored material |
| JP4502357B2 (en) | 2002-03-08 | 2010-07-14 | キヤノン株式会社 | Novel compound and its synthesis method, ink, ink cartridge, recording unit, ink jet recording apparatus and recording method |
| AU2005279193B2 (en) * | 2004-08-30 | 2010-09-30 | Basf Se | Shading process |
| US7446926B2 (en) * | 2004-09-27 | 2008-11-04 | Idc, Llc | System and method of providing a regenerating protective coating in a MEMS device |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8421558D0 (en) * | 1984-08-24 | 1984-09-26 | Ici Plc | Water-soluble dye |
| JPH0277983A (en) * | 1988-09-14 | 1990-03-19 | Toshiba Corp | Graphic tracking system |
| JPH0338587A (en) | 1989-07-03 | 1991-02-19 | Doujin Kagaku Kenkyusho:Kk | Labeling compound catalyzing oxidation reaction |
| DE4202038A1 (en) * | 1992-01-25 | 1993-07-29 | Basf Ag | USE OF A LIQUID CONTAINING IR DYES AS PRINTING INK |
| JP3744981B2 (en) | 1995-09-14 | 2006-02-15 | オリヱント化学工業株式会社 | Novel phthalocyanine or naphthalocyanine derivative |
| US5759254A (en) * | 1996-07-18 | 1998-06-02 | Ciba Specialty Chemicals Corporation | Substituted phthalocyanines |
| JP3475249B2 (en) * | 1996-07-25 | 2003-12-08 | 株式会社リコー | Recording liquid and recording method using the same |
| GB9708532D0 (en) * | 1997-04-26 | 1997-06-18 | Zeneca Ltd | Phthalocyanine ink-jet dyes |
| JP3446212B2 (en) * | 1998-03-26 | 2003-09-16 | セイコーエプソン株式会社 | Ink composition and ink set for realizing an image with excellent light fastness |
| GB9817236D0 (en) * | 1998-08-08 | 1998-10-07 | Zeneca Ltd | Compound,composition and use |
-
2000
- 2000-04-25 EP EP00917456A patent/EP1174432A1/en not_active Withdrawn
- 2000-04-25 CN CN00806641A patent/CN1348456A/en active Pending
- 2000-04-25 US US09/958,554 patent/US6589325B1/en not_active Expired - Fee Related
- 2000-04-25 CA CA002367738A patent/CA2367738A1/en not_active Abandoned
- 2000-04-25 WO PCT/JP2000/002696 patent/WO2000064901A1/en not_active Application Discontinuation
- 2000-04-25 KR KR1020017012919A patent/KR20020002423A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107835843A (en) * | 2015-07-01 | 2018-03-23 | 日本化药株式会社 | Dispersible pigment dispersion, colored resin composition and optical filter containing organic coloring pigments and infrared absorbing dye |
| CN107835843B (en) * | 2015-07-01 | 2021-03-19 | 日本化药株式会社 | Pigment dispersion liquid containing organic coloring pigment and infrared absorbing dye, colored resin composition, and optical filter |
Also Published As
| Publication number | Publication date |
|---|---|
| US6589325B1 (en) | 2003-07-08 |
| EP1174432A1 (en) | 2002-01-23 |
| WO2000064901A1 (en) | 2000-11-02 |
| KR20020002423A (en) | 2002-01-09 |
| CA2367738A1 (en) | 2000-11-02 |
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